US3651147A

US3651147A - 1 6-diphosphatriptycene

Info

Publication number: US3651147A
Application number: US78962A
Authority: US
Inventors: Kurt Weinberg
Original assignee: Union Carbide Corp
Current assignee: Union Carbide Corp
Priority date: 1970-10-07
Filing date: 1970-10-07
Publication date: 1972-03-21
Anticipated expiration: 1989-03-21

Abstract

THIS INVENTION RELATES TO THE PRODUCTION OF 1,6-DIPHOSPHATRIPTYCENE WHICH COMPOUND IS USEFUL AS A PLASTICIZER, FLAME RETARDANT, INTERMEDIATE, A LIGAND IN HOMOGENEOUS CATALYSIS AND A REACTION INTERMEDIATE IN THE PRODUCTION OF INSECTICIDE FUEL AND OIL ADDITIVES.

Description

3,651,147 1,6-D1PHOSPHATRIPTYCENE Kurt Weinberg, Upper Saddle River, N..l'., assignor to Union Carbide Corporation, New York, N.Y.

N Drawing. Continuation-impart of application Ser. No. 621,763, Mar. 9, 1967, now Patent No. 3,557,207. This application Oct. 7, 1970, Ser. No. 78,962

Int. Cl. (107E 9/50 US. Cl. 260-606.5 P 1 Claim ABSTRACT OF THE DISCLOSURE This invention relates to the production of 1,6diphosphatriptycene which compound is useful as a plasticizer, flame retardant intermediate, a ligand in homogeneous catalysis and a reaction intermediate in the production of insecticide fuel and oil additives.

This application is a continuation-in-part of my copending application, Ser. No. 621,763, filed Mar. 9, 1967, now US. Pat. No. 3,557,207.

The invention relates to a process for the production of arylphosphine halide by reacting an aryl halide with White phosphorous in the presence of a catalytic amount of a Lewis acid.

Arylphosphine halides are valuable compositions that can be used as plasticizers, as flame retardants, and as reaction intermediates in the production of a wide variety of useful compositions such as insecticides, fuel and oil additives, and the like. Heretofore, however, there has been no satisfactory economic method for the production of this class of compositions. To illustrate, some recent preparations of arylphosphine halides include the conversion of primary phosphinic acids to arylphosphine halides by reaction with phosphorus trichloride, as disclosed by Frank, J. Org, Chem. 26, 850 (1961). Another preparation of arylphosphine halides was disclosed by Becker in U.S. Pat. No. 3,036,132. This method involved the reaction of phosphorus trichloride with M(AlR Where M is an alkali metal and R is aryl. Maier, in Helv. Chin. Acta. 46, 2026 (1963), reported the reaction of elemental phosphorus with bromobenzene at 350 C. to obtain diphenylphosphine bromide and phenylphosphine dibromide, the corresponding reaction with chlorobenzene, however, did not produce any arylphosphine halides. In US. Pat. No. 3,057,917, Maier discloses another method for the production of arylphosphine halides. In this patent, Maier reacts vaporized arylhalide with red phosphorus in the presence of major amounts of a metallic catalyst such as copper. This patent states that the use of red phosphorus is preferred, thereby implying that other forms of elemental phosphorus can also be used. However, in the paper which was cited above, Maier pointed out that the reaction of methyl bromide with white phosphorus produced only traces of methylphosphine dibromide. Thus, it seems apparent that the more economical white phosphorus cannot be used in Maiers process because the yields of desired product are too low. All of the processes described above are relatively 3,651,147 Patented Mar. 21, 1972 ICC undesirable because none is an economical method for producing arylphosphine halides.

The present invention provides a useful and economical process for the production of arylphosphine halides. The inventive process comprises reacting an aryl halide with white phosphorus in the presence of a catalytic amount of a Lewis acid.

White phosphorus is employed as a reactant in this invention. The second reactant that is employed in the process of the invention is an aryl halide. The aryl halides that are employed can be represented by the formula RX wherein R represents an aryl radical or an alkaryl radical, preferably a hydrocarbon aryl or alkaryl radical, having from 6 up to 10 or more carbon atoms and having a valence of 11, wherein X represents a halo group, preferably a bromo, chloro, or iodo group, and wherein n represents a number having a value of from 1 to 3. Specific illustrative aryl halides include chlorobenzene, bromobenzene, iodobenzene, fiuorobenzene, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzenes, o-chlorotoluene, m-chlorotoluene, 2,4-dichlorotoluene, l-chloronaphthalene, l-bromonaphthalene, bromotoluenes, iodotoluenes, l-iodonaphthalene, and the like.

The catalysts that are employed in the process of the invention are metal halide Lewis acids. Specific illustrative examples of these catalysts include stannic tetrachloride, titanium tetrachloride, aluminum triiodide, ferric triiodide, aluminum trifiuoride, ferric trifiuoride, aluminum trichloride, aluminum tribromide, ferric trichloride, ferric tribromide, and the like. The preferred catalysts include ferric trichloride, aluminum trichloride, aluminum tribromide, and ferric tribromide.

The proportions of the reactants that are employed in the process of this invention are not narrowly critical. For example, the mole ratio of white phosphorus (P ):aryl halide can vary from about 1:1/2 to 1:60, preferably from about 1:2 to 1:12, and more preferably from about 1:4 to about 1:6. The Lewis acid catalyst is employed in small catlytic quantities. For example, the catalyst can be employed in a proportion of from about 0.1 weight percent to about 3 weight percent, and preferably from about 0.2 weight percent to about 1.5 weight percent, based upon the total weight of the reactants.

The process of the invention is carried out at elevated temperatures. The exact temperature employed is dependent somewhat upon the particular nature of the aryl halide reactant. For example, when an aryl chloride is the reactant, the operable temperature range is normally from about 280 C. to about 420 C., preferably from about 300 C. to about 400 C. and more preferably from about 330 C. to 360 C. When the aryl halide is in aryl bromide, the temperature then can be employed will normally be within the range of from about 200 C. to about 450 C., preferably within the range of from about 250 C. to about 370 C., and more preferably from about 280 C. to about 300 C. When the aryl halide is an aryl iodide, the temperature range is preferably somewhat below the temperatures indicated for aryl bromides, for example, preferably from about 250 C. to about 290 C. When the aryl halide is an aryl fluoride, somewhat 3 higher temperatures than those indicated for aryl chloride should preferably be employed. For example, a pre ferred temperature range when the aryl halide reactant is an aryl fluoride will be from about 400 C. to about 450 C.

The process of the invention is carried out for a period of time sufilcient to produce an arylphosphine halide. The exact reaction time is dependent, in part, upon factors such as the exact nature of the reactant, the reaction temperature, and the like. For example, reaction times of from about 1 to about 50 hours can be employed, preferably from about 4 to about 26 hours, and more preferably from about 6 to about 12 hours.

The process of the invention can be carried out, for example, by adding the reactants and catalyst to a suitable reaction vessel and maintaining the mixture at the elevated reaction temperature for a period of time sufficient to produce an arylphosphine halide. If desired, the reaction can be carried out in an inert, normally liquid, reaction medium such as a high-boiling aliphatic, aromatic or cycloaliphatic hydrocarbon. However, the use of an inert organic reaction medium is entirely optional. It is in general preferred to carry out the reaction under an inert atmosphere of nitrogen, or the like. The reaction can be carried out under atmospheric pressure, superatmospheric pressure, or even subatmospheric pressure, which ever is more convenient. However, the exact pressure that will be employed is dictated to a degree by the boiling points of the aryl halide reactant, or by the boiling point of any inert reaction medium that is employed. The reaction can be carried out by gently agitating the reactants during the reaction period, and at the close of the reaction period, by cooling the reaction mixture and then separating the products by conventional methods such as by fractional distillation. The distillation will preferably be carried out under vacuum because many of the products of the reaction have relatively high boiling points.

Any suitable conventional reaction 'vessel can be employed for the process of the invention. The equipment should have means for heating, means for agitation, and means for cooling the reaction at the conclusion of the reaction period.

The process of the invention produces useful arylpbosphine halides that are usually a mixture of an arylphosphine dihalide and a diarylphosphine monohalide. Among the useful and valuable compositions that can be produced by the process of the invention there can be named phenylphosphine dichloride, diphenylphosphine monochloride, (o-chlorophenyl)phospine dichloride, bis(ochlorophenyl phosphine monochloride, l-naphthylphosphine bromides, chlorotolylphosphine, chlorides, dichlorotolylphosphine chlorides, and many other useful compositions. These compositions are useful per se as plasticizers and flame retardant additives for many types of plastics such as vinyl chloride polymers, urethane polymers, phenolic resins, and the like. The compositions that are produced by the process of the invention are also useful as reactions intermediates for the porduction of insecticides, lubricant oil additives, fuel additives, and the like.

The examples which follow illustrate the invention.

EXAMPLE 1 Preparation of phenylphosphine dichloride and diphenylphosphine monochloride from white phosphorus and chlorobenzene Phosphorus (6.3 g.), chlorobenzene (45 g.) and aluminum chloride (0.7 g.) were charged to a glass tube of 12-inch length and As-inch I.D. After sealing, the tube was heated to about 350 C. in a 3-liter autoclave which was filled with 650 ml. of n-propanol and pressurized with 500 pounds of nitrogen. The reaction mixture was kept at that temperature (between 340 and 360 C.) for 8 hours. After cooling in liquid nitrogen, the tube was opened, its contents transferred to a distillation flask and distilled in vacuo.

Yields:

(1) 18.0 g. of phenylphosphine dichloride BP: 5055 C./0.5 mm. Hg

49.6% of theory (based on phosphorus) (2) 15.5 g. of diphenylhposphine monochloride BP: 122 C./0.5 mm. Hg

34.7% of theory (based on phosphorus) (3) 8.6 g. of unreacted chlorobenzene Combined yields of phenylphosphine dichloride and diphenylphosphine monochloride: 84.3% of theory (based on phosphorus).

EXAMPLE 2 Preparation of (o-chlorophenyl)phosphine dichloride and di (o chlorophenyl)phosphine monochloride from white phosphorus and o-dichlorobenzene Phosphorus (6.3 g.), o-dichlorobenzene (60 g.) and ferric chloride (0.9 g.) were charged to a glass tube of 12-inch length and 45-inch I.D. After sealing, the tube Was heated to about 326 C. in a 3-liter autoclave which was filled with 650 ml. of n-propanol and pressurized with 500 pounds of nitrogen. The reaction mixture was maintained at this temperature (317-332") for 8 hours. After cooling in liquid nitrogen the tube Was opened, its contents transferred to a distillation flask and distilled in vacuo.

Yields:

( 1) 12.85 g. of o-chlorophenylphosphine dichloride BP: 71-73 C./0.550.65 mm. Hg 30.0% of theory (based on phosphorus) (2) 9.42 g. of di-(o-chlorophenyl)phosphine monochloride BP: 147-153 C./0.5 mm. Hg 16.4% of theory (based on phosphorus) (3) 26.7 g. of unreacted o-dichlorobenzene Combined yields of o-chlorophenylphosphine dichlo- 1ide+di(o-chlorophenyl) phosphine monoc-hloride: 46.4 of theory (based on phosphorus).

EXAMPLE 3 Preparation of l-naphthylphosphine dibromide and di- -(1 naphthyl)phosphine monobromide from white phosphorus and l-bromonaphthalene Phosphorus (6.3 g.), l-bromonaphthalene (86 g.) and anhydrous ferric chloride (0.9 g.) were refluxed under nitrogen in a reaction flask fitted with an air cooled condenser for 6 hours at atmospheric pressure. After cooling to room temperature the reaction mixture was transferred to a distillation kettle and distilled in vacuo.

Yields:

(1) 23.08 g. of 1 naphthylphosphine dibromide MP:

7679 C. (Yield: 26.2% of theory (based on phosphorus) (2) 13.21 g. of di-(l-naphthyDphosphine monobromide MP: ISO-152 C. BP: 240 C./0.5 mm. Yield: 18.1% of theory (based on phosphorus) (3) 17.47 g. of unreacted l-bromonaphthalene Combined yields of l-naphthylphosphine dibromide and di (l naphthyl)phosphine bromide: 54.3% of theory (based on phosphorus).

EXAMPLES 4 TO 12 The reactions were run in the same equipment as described in Example 1 and also worked up in the same way. The results are summarized in the following Table I. In order to show the effect of the catalyst on the reaction, a number of experiments were carried out without catalyst (Examples 4, 7, 9, and 11) for comparison with those carried out in the presence of catalysts.

TABLE I Mole ratio of Reaction Yields Example Temp, phos horns: irne, inpercent Number Aryl halide Catalyst O my halide hours Products of theory 4 None 318-382 1/212 1tlafilaaaaaiaaa abitat?:11;;;; at di-(p-Chlorophenyl) hosphine chloride 16.0 5 p Dichlombenzene" 318 332 1/2'2 8 {g cklleirtiphinglphtbsgtllrine dichlofilidea 20.2 1- oehyp any p 05 hinec ori 13.6 6 O Dlchlorotoluene"" 326-338 1/22 8 lgihlethhiylgh%nlylphtli)splhingldichloridea. 27. 1 e yp eny p osp ine eh ori e 0 7 0 Chlorotoluene None 313 332 1/2'2 8 {oi-L (Ietliylplheii filphoiphine diehlorliliiag1 0 imat ypieny phosphinec ori a. 16.1 8 m chlorotoluene 318 332 1/22 8 ig-ivletlliylphiantylphiifpkhine dichlorllde 16. rne by p any p osphine ch ori 0 9 None 318-332 8 im-Methylphenylphosphine dichloride". 0 10 2,4 diehlorotoluene F6013"-.- 318-332 1 22 s f' jf (3-chloro4-methylphenyl) phosphine dichloride. 11 .,do one... 318-332 1/222 M V 8 diiw -ehloro-4-methylpheny1)phosphine chlo- 0 r e. (3gglorot-methylphenyl) phosphine dichlo- 0 12 1-chloronaphtha1ene FeCl 326-338 1/2z2 8 di-(l-naphthyl)phosphine chloride 9.7 (l-naphthyDphosphine dichloride 40. 2

I have also discovered a novel composition of matter which can be produced according to the above general reaction scheme by employment of select reactants under select conditions. The novel composition of matter, 1,6- diphosphatriptycene (5,10 o-benzo 5,10 dihydrophosphanthrene) can be represented by the following struc- This compound has utility as a plasticizer, flame retardant intermediate, as a ligand in homogeneous catalysts, and as a reaction intermediate in the production of a wide variety of useful compositions such as insecticides, fuel and oil additives, and the like.

The following example will illustrate preparation of the novel compound.

EXAMPLE 13 A tube capable of being sealed was used as the reaction vessel and received 70 grams of white phosphorus, 585 grams of o-dichlorobenzene and one gram of anhydrous ferric chloride as the catalyst therefor. The tube was sealed and heated at 280 C. for a period of 5 hours. The resulting reaction mixture consisted of a dark crystalline substance and a liquid layer which was a mixture of ochlorophenyl phosphine dichloride, di-(o-chlorophenyl) phosphine chloride, phosphorus trichloride and unreacted o-chlorobenzene.

Filtration was employed to separate the crystalline substance from the liquids. Methanol washing followed by recrystallization from tetrachloroethylene was used to purify the crystalline substance. A further quantity of the crystalline material was obtained in the distillation of the liquid products. The purified product melted at 323-325 C. Gas chromatographic analysis (15% SE- on Chromosorb W at 275 C.) revealed that in addition to the main product, an impurity in an amount of about 6% was present. This impurity was removed by further recrystallization from tetrachloroethylene.

Elemental analysis suggested that the compound had the empirical chemical formula C H P The analysis was as follows:

Calculated (percent): C, 74.46; H, 4.14; P, 21.35. Found (percent): C, 74.12; H, 4.07; P, 21.19.

The mass spectrum of the compound showed a strong parent peak at 290.

The NMR spectrum showed 2 groups of aromatic protons and the areas under the peaks indicated that both groups of protons are present in equal numbers, one group belonging to the protons in the ortho-position in each of the P-atoms and the other group belonging to the corresponding protons in the m-position to the P-atoms.

The total yield of 1,6-diphosphatriptycene was about 20% based on phosphorus.

What is claimed is:

1. As a new composition of matter, 1,6-diphosphatriptycene.

References Cited UNITED STATES PATENTS 3,064,055 11/1962 Herring 260-606.5 P 3,400,163 9/1968 Mason et al. 260-6065 P 3,401,204 9/1968 Mason et a1 260-6065 P 3,435,076 3/1969 Mason et al. 260606.5 P 3,440,291 4/1969 Winkle et a1. 260-606.5 P 3,502,730 3/1970 Mason et a1. 260606.5 P

OTHER REFERENCES Hoffman, Chemical Abstracts, vol. 62 (1965), pp. 14719-14721.

JAMES E. POER, Primary Examiner W. F. W. BELLAMY, Assistant Examiner US. Cl. X.R. 252-8.1